JPH0862759A - Silver halide photographic sensitive material and image forming method using same - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material capable of obtaining an extremely high-contrast photographic characteristics by using a stable developing solution and the method for forming an ultrahigh-contrast negative image by using it. CONSTITUTION: This silver halide photographic sensitive material contains at least one of compounds represented by formulae I and II in which A is a group for promoting adsorption to silver halide or its precursor; B is a quaternized N-containing heterocyclic group and its counter ion; L is a bonding group; (m) is 0 or 1; and (n) is an integer of 1-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a method for forming a high-contrast image using the same, and more particularly to a silver halide photographic light-sensitive material with controlled gradation.

[0002]

2. Description of the Related Art Halftone dot images (doti
mage) for continuous tone reproduction or line drawing reproduction
In order to be successful, there is a need for an imaging system that exhibits ultrahigh contrast photographic properties. Conventionally, a special developer called a lith developer has been used for this purpose. The lith developer contains only hydroquinone as a developing agent, and a sulfite salt used as a preservative is used in the form of an adduct with formaldehyde so as not to impair the infectious developability, and the concentration of free sulfite ion is extremely low. (Usually 0.1 mol / liter or less) and high pH (substantially pH 1
1) or more), the desired performance cannot be obtained. Therefore, the lith developer has a serious drawback that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days. Therefore, when the processing stability is emphasized and the processing is carried out with a general black and white developing solution, the stability of the developing solution is remarkably improved. It had a problem that it was inferior to the case. Further, U.S. Pat. No. 2,419,975 describes that a certain kind of hydrazine compound is added to a silver halide emulsion to obtain a hard negative image, which is specifically shown in this patent specification. In order to obtain a super-high contrast (γ ≧ 10) negative image using the hydrazine compound described above, a developer having a high pH of 12.8 must be used. But,
A strong alkaline developer having a pH close to 13 is easily oxidized by air and is unstable, and cannot withstand long-term storage and use. Of course, if the content of sulfite ion is increased, the storage stability will be improved, but in order to sufficiently improve the stability of such a high pH developer, it is necessary to add a large amount of sulfite, resulting in contamination of the processing solution. In addition to the above, there is a serious problem that the image becomes harder. Therefore, there has been a demand for an image forming system which does not have the above-mentioned drawbacks and which has an ultrahigh contrast and has a good storability of the processing liquid.

In order to meet such demands, US Pat. Nos. 4,224,401, 4,168,977, 4,166,742, 4,311,781 and 4,272,606, Nos. 4,221,857, 4,243,739, and the like, which are described in US Pat.
A surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound not described in JP-A No. 9,975 is processed with a stable developing solution having a pH of 11.0 to 12.3 to give a γ of 10 A system for forming a super-high contrast negative image has been proposed. However, the above-mentioned image forming system is a so-called rapid access process (that is, an extremely quick photographic process, which has been in increasing demand in recent years, and usually from the start of the process to the process of obtaining a dried film. Total processing time 90 ~ 1
20 seconds, of which 15 to 15 hours are allotted for development
However, there is a problem that it is difficult to obtain a super-high contrast image for 60 seconds).

On the other hand, for a high-contrast silver halide emulsion, for example, British Patent No. 775,197 and US Pat.
No. 31,289 describes an emulsion in which a rhodium salt is added to form grains, but the degree of contrast increase by the rhodium salt is insignificant (according to Example 1 of the above-mentioned US patent,
The contrast of 2.60 is only increased to 3.20), and if the amount of rhodium is further increased, the blackening density (Dens
It was not possible to achieve a super-high contrast image required for a silver halide photographic light-sensitive material for photoengraving due to a decrease in the (ity max).

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a photographic characteristic of a hard negative tone using a stable developing solution and an image forming method using the same. Is to provide.

[0006]

The object of the present invention is to use a silver halide photographic light-sensitive material and a photographic light-sensitive material containing a compound represented by the following general formula (I) or (II). Was achieved by a different imaging method.

[0007]

[Chemical 3]

In the formula, A is an adsorption promoting group on silver halide,
Alternatively, it represents a precursor thereof, and B represents a quaternized nitrogen-containing heterocycle and its counter ion. L represents a linking group, m represents 0 or 1, and n represents an integer of 1 to 4.

The compound represented by formula (I) or (II) used in the present invention will be described in more detail. Specific examples of the adsorption promoting group for silver halide represented by A in the general formula (I) or (II) include a thioamide group, a mercapto group (-SH), an aromatic group having a mercapto group or a heterocyclic group. , A nitrogen-containing heterocyclic group containing two or more N atoms, one of which is bonded to at least a hydrogen atom, or a precursor of these groups. Preferred examples of the group represented by A include a mercapto group (-S
H), a mercaptophenyl group, a heterocyclic group having a mercapto group (for example, 2-mercapto-1-thia-3,4-diazolyl group, 2-mercapto-tetrazolyl group, 2-mercapto-1,3,4-triazolyl group , 2-mercapto-benzoxazolyl group, 2-mercapto-benzothiazolyl group, 2-mercaptopyridyl group, 4-mercapto-1,3,3a, 7-tetrazaindenyl group, etc.),
A benzotriazolyl group, a thiatriazolyl group, a thioureido group (for example, an unsubstituted thioureido group, an N'-phenylthioureido group, N and N'are both linking groups represented by L in the general formula (I) or (II)). A substituted thioureido group, etc.), a thiourethane group (eg, phenylthiourethane group, cyclohexylthiourethane group, etc.) or a precursor of these groups.

The term "precursor" as used herein means a precursor capable of promptly producing these groups by the developing solution when it is treated with the developing solution. As the precursor, the hydroxide contained in the developing solution is used. ion (OH ^-) by or sulfite ions (SO ₃ ^2-) and the like, either hydrolyzed or cross oxidation with an oxidized product of a developing agent generated in the image-wise as triggers, are degraded by development processing solution Those are preferable. Specifically, for the former, for example, an alkoxycarbonyl group, an aryloxycarbonyl group, an N, N-disubstituted carbamoyl group, an acyl group,
1,3,3a, 7-tetrazainden-4-yl group, the following uracil group

[0011]

[Chemical 4]

And the like. For the latter,
Examples thereof include groups represented by general formula (a).

[0013]

[Chemical 5]

In the general formula (a), Y ₃ represents a substituent, preferably an N'-substituted ureido group, an acylamino group, a sulfonamide group or an alkylthio group. The group represented by A in the general formula (I) or (II) is
Besides being bonded to the group represented by {(L) _m -B} at any position, it may be substituted with any substituent.

In the present invention, the substituent represents a halogen atom, or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. As the group bonded by a carbon atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group,
An aryloxycarbonyl group, an acyl group, a carboxyl group, a cyano group, or a heterocyclic group, which is bonded by an oxygen atom, is a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a sulfonyl group. An oxy group having a nitrogen atom bonded thereto includes an acylamino group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, and an aryloxycarbonylamino group. , A sulfonamide group, an imide group, a heterocyclic group, as a sulfur atom bonded as an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfonyl group, a sulfo group, Sulfini Group, and the like. These may be further substituted with these substituents.

The substituent will be described in more detail. The halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl and t.
-Butyl, benzyl, cyclopentyl. The alkenyl group has 2 to 16 carbon atoms, such as vinyl,
1-propenyl, 1-hexenyl, styryl and the like can be mentioned. The alkynyl group has 2 to 16 carbon atoms,
Examples thereof include ethynyl, 1-butynyl, 1-dodecenyl, phenylethynyl and the like. The aryl group is an aryl group having 6 to 24 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl.

The carbamoyl group has 1 to 18 carbon atoms, and examples thereof include carbamoyl, N-ethylcarbamoyl, N-octylcarbamoyl and N-phenylcarbamoyl. 2 carbon atoms as an alkoxycarbonyl group
~ 18, for example, methoxycarbonyl, benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 18 carbon atoms and is, for example, phenoxycarbonyl. The acyl group has 1 to 18 carbon atoms, and examples thereof include acetyl and benzoyl. The heterocyclic group linked by a carbon atom on the ring is a 5- or 6-membered saturated or unsaturated heterocycle having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, The number of heteroatoms constituting the ring and the number of kinds of elements may be one or more, for example, 2-furyl, 2-thienyl,
2-pyridyl and 2-imidazolyl.

The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms and is, for example, methoxy, 2
-Methoxyethoxy and 2-methanesulfonylethoxy. The aryloxy group has 6 to 24 carbon atoms and includes, for example, phenoxy, p-methoxyphenoxy, m-
(3-hydroxypropionamide) phenoxy. The heterocyclic oxy group is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. The number of atoms and the number of elements may be one or more, and examples thereof include 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy,
It is 2-pyridyloxy. The acyloxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-hexylcarbamoyloxy and N-phenylcarbamoyloxy. The sulfonyloxy group has 1 to 1 carbon atoms
And 6 are, for example, methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 16 carbon atoms,
Preferred are those having 1 to 10 carbon atoms, such as acetamide and p-chlorobenzoylamide. The alkylamino group has 1 to 16 carbon atoms, preferably 0 to 1 carbon atoms.
And, for example, N, N-dimethylamino, N- (2-
Hydroxyethyl) amino. The arylamino group has 6 to 24 carbon atoms and is, for example, anilino or N-methylanilino. The heterocyclic amino group is a 5-membered or 6-membered saturated or unsaturated heterocyclic amino group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms and constitutes a ring. The number of heteroatoms and the kinds of elements to be used may be one or more, for example, 2-oxazolylamino, 2-tetrahydropyranylamino,
It is 4-pyridylamino. The ureido group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and includes, for example,
Ureido, methylureido, N, N-diethylureido, and 2-methanesulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
-16, preferably those having 0-10 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, and is, for example, methoxycarbonylamino group. Aryloxycarbonylamino group has 7 to 24 carbon atoms
Such as phenoxycarbonylamino, 2,6
-Dimethoxyphenoxycarbonylamino. The sulfonamide group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and includes, for example, methanesulfonamide, p
-Toluenesulfonamide. The imide group has 4 to 16 carbon atoms, and includes, for example, N-succinimide, N
-Phthalimide. The heterocyclic group linked by a ring nitrogen atom is a 5- to 6-membered heterocycle consisting of at least one kind of carbon atom, oxygen atom or sulfur atom and a nitrogen atom, and examples thereof include pyrrolidino, morpholino and imidazolino.

The alkylthio group has 1 to 16 carbon atoms,
Preferred are those having 1 to 10 carbon atoms, such as methylthio and 2-phenoxyethylthio. The arylthio group has 6 to 24 carbon atoms, and examples thereof include phenylthio and 2-carboxyphenylthio. The heterocyclic thio group is a 5-membered or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and which constitutes a ring. The number of atoms and the number of elements may be one or plural, and examples thereof include 2-benzothiazolylthio and 2-pyridylthio.

The sulfamoyl group has 0 to 1 carbon atoms
6, preferably those having 0 to 10 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsulfamoyl. Alkoxysulfonyl group has 1 carbon
To 16, preferably 1 to 10 carbon atoms, for example, methoxysulfonyl. The aryloxysulfonyl group has 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, and is, for example, phenoxysulfonyl. The sulfonyl group has 1 to 16 carbon atoms, preferably 1 to 1 carbon atoms
0, such as methanesulfonyl and benzenesulfonyl. The sulfinyl group has 1 to 16 carbon atoms,
Preferred are those having 1 to 10 carbon atoms, such as methanesulfinyl and benzenesulfinyl.

The substituent in the present invention is preferably
Alkyl group, aryl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, cyano group, alkoxy group, aryloxy group, carbamoyloxy group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino Base,
A sulfonamide group, a sulfamoyl group and a sulfonyl group are more preferable, and an alkyl group, an aryl group, a carbamoyl group, an alkoxy group, an acylamino group, a ureido group, a sulfonamide group and a sulfamoyl group are more preferable.

B in the general formula (I) or (II)
Represents a quaternized nitrogen-containing heterocyclic group and its counter ion. Specifically, the structure of the quaternary salt portion is as follows:
Examples thereof include pyridinium salts, quinolinium salts, isoquinolinium salts, phenanthrinium salts, triazolinium salts, imidazolinium salts, benzothiazolinium salts, and the like. B also represents a bis or tris cationium compound and a counterion thereof in which a plurality of these quaternary salts are linked, in which case each quaternary salt may be the same or different, and Are linked by any linking group. The group represented by B in the general formula (I) or (II) can be linked to the group represented by {(L) _m -A} at any position, but it may be substituted with any other substituent. May be.

However, when the substituent bonded to the nitrogen atom of the nitrogen-containing heterocycle to form a quaternary salt or the substituent bonded to the carbon atom adjacent to the nitrogen atom represents an alkyl group, the alkyl group is α No alkynyl group is bound to the position or a carbonyl group, a hydrazino group or an imino group is bound to the β-position. When the quaternized nitrogen-containing heterocyclic group represented by B has such a substituent, such a compound is disclosed in JP-A-62-291637.
This is because, as disclosed in JP-A No. 1994-163, it exhibits a non-imagewise fogging effect on unexposed silver halide, revealing properties unfavorable for the purpose of the present invention.

The examples of the substituent represented by B are the same as those described above as the examples of the substituent in the present invention except the above-mentioned restrictions, and the preferable range is also the same.

The group represented by B in the general formula (I) or (II) is preferably the following general formula (b),
It is represented by (c) and (d).

[0028]

[Chemical 6]

In the formula, Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q ₅ are
It represents a group of non-metal atoms capable of forming a nitrogen-containing heterocycle with a nitrogen atom, and R ₁₁ , R ₁₂ and R ₁₃ each represent a substituent capable of binding to a quaternized nitrogen atom. W ₁ and W ₂ represent a linking group, i represents 0 or 1, and X ⁻ represents a counter anion. Q ₂ and Q ₃ , Q ₄ and Q ₅ , or R ₁₂ and R ₁₃ may be the same or different from each other. Specific examples of the quaternized nitrogen-containing heterocyclic ring formed by Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q ₅ together with the nitrogen atom, and preferred examples thereof are shown in the above general formula (I) or (II). This is the same as the specific example described for B. Q ₁ ,
The structure of the quaternary salt formed by Q ₂ , Q ₃ , Q ₄ and Q ₅ together with the nitrogen atom is particularly preferably when they represent a pyridinium salt, an isoquinolinium salt or a quinolinium salt, and most preferably a pyridinium salt. It's time.

The groups represented by the general formulas (b), (c) and (d) can be linked to the group represented by ({(L) _m -A}) at any position, and Other than the above, it may be substituted with any substituent, provided that when the substituent is bonded to a carbon atom adjacent to the quaternary nitrogen atom, or R ₁₁ , R ₁₂ and R ₁₃ are substituted with these substituents. When the group represents an alkyl group, the alkyl group does not bind an alkynyl group at the α-position or a carbonyl group, a hydrazono group or an imino group at the β-position R ₁₁ ,
Preferable examples of R ₁₂ and R ₁₃ are an alkyl group, an aryl group and a heterocyclic group excluding the above restrictions, and particularly preferably a substituted or unsubstituted alkyl group excluding the above restrictions.

When R ₁₁ , R ₁₂ and R ₁₃ represent an alkyl group, the alkyl group is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms. Methyl, ethyl, propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, phenamyl, 4
-Methylbenzyl, 2-methanesulfonamidoethyl,
2-Methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl.

Next, the counter ion will be described. The counter ion is a counter ion for charge balance, and is a cation when it has two or more anionic groups in the molecule. Examples of the anion include chlorine ion, bromine ion, iodine ion, p-toluenesulfonate ion, sulfate ion, perchlorate ion, trifluoromethanesulfonate ion, boron tetrafluoride ion, phosphorus hexafluoride ion and the like. As the cation, for example, sodium ion,
Potassium ion, lithium ion, calcium ion,
They are ammonium ion, tetrabutylammonium ion and triethylammonium ion. There is no counterion when forming an intramolecular salt.

The linking group represented by L in the general formula (I) or (II) is a divalent or trivalent linking group,
A group connecting A and B, two A and B, or A and two B. The divalent linking group is an atom or atomic group containing at least one of C, N, S and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NH-,
-N =, - CO -, - SO 2 - ( may have these groups the substituents), it is made of a single or a combination thereof and the like. As an example of the combination, -COO-,
_{-CONH -, - SO 2 NH -} , - OCONH -, - N
_{HCONH-, NHSO 2 NH -, -} ( alkylene) -
CONH -, - (arylene) -SO ₂ NH -, - CO
O- (alkylene)-, -CONH- (alkylene)
-, - SO ₂ NH- (alkylene) -, - NHCONH
-(Alkylene)-, -CO- (alkylene)-, -O
-(Alkylene)-,-(alkylene) -NHCONH
-, -S- (alkylene)-and the like are preferable.

Examples of the trivalent linking group include a trisubstituted ureido group, a trisubstituted amino group, a trisubstituted methine group, a disubstituted carbamoyl group, a disubstituted urethane group, a disubstituted sulfamoyl group and a disubstituted sulfamoylamino group. , And the like, but of these, a trisubstituted ureido group, a disubstituted carbamoyl group, and a disubstituted sulfamoyl group are particularly preferable.

In the general formula (I) or (II), m
Represents 0 or 1, and n represents an integer of 1 or 4, particularly preferably m is 0 or 1, and n is 1 or 2.

Specific examples of the compound of the present invention will be given below, but the present invention is not limited thereto.

[0037]

[Chemical 7]

[0038]

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[0039]

[Chemical 9]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

The compound represented by formula (I) or (II) of the present invention can be synthesized by various known methods. Since the optimum synthetic method is selected depending on the individual compound, it is not possible to cite a particularly general synthetic method. Among them, some examples of useful synthetic routes are shown below.

[0045]

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[0046]

[Chemical 15]

(Synthesis Example) 1. Synthesis of Exemplified Compound I-2 8.7 g of 1,3-dichloropropane and 4.0 g of 4-phenylpyridine were dissolved in 50 ml of dimethylacetamide and heated at 130 ° C. for 4 hours. After allowing the reaction solution to cool, ethyl acetate was added to the reaction solution in which salt had precipitated to increase the salt content,
The precipitated crystals were collected by filtration. Obtained N- (3-chloropropyl) -4-phenylpyridinium chloride 3.6
3 g and 2,5-dimercapto-1,3,4-thiadiazole 2.14 g were suspended in acetonitrile and heated under reflux. Further, 1.2 ml of pyridine was added dropwise to the reaction solution and the reaction was carried out for 3 hours. After allowing the reaction solution to cool, the precipitated salt is collected by filtration,
This was treated with alkaline water to obtain an inner salt. This was dissolved in methanol with heating and then treated with dilute hydrochloric acid to recrystallize, thereby obtaining 3.2 g of the target Exemplified Compound 2.

2. Synthesis of Exemplified Compound I-3 In the synthesis of Exemplified Compound I-2, 3-carbamoylpyridine was used instead of 4-phenylpyridine, and 1,3
The target Exemplified Compound 3 could be synthesized in exactly the same manner except that 1,8-dichlorooctane was used instead of -dichloropropane.

3. Synthesis of Exemplified Compound I-23 3-Chloropropylamine hydrochloride 13.0 g and 4-phenylpyridine 15.5 g were dissolved in dimethylacetamide and heated at 70 ° C. for 5 hours. Ethyl acetate was added to this, and the precipitated crystals were collected by filtration to obtain 17.5 g of 3- (4-phenylpyridyl) -propylamine hydrochloride. This was treated with 5-phenoxycarbonylaminobenzotriazole 1
5.8 g and 12.6 g of imidazole were dissolved in 100 ml of dimethylacetamide, 8.7 ml of triethylamine was further added, and the mixture was heated at 60 ° C. for 6 hours. By the usual post-treatment operation, 8.36 g of the desired exemplary compound was obtained.

The amount of the compound of the general formula (I) or (II) of the present invention to be added is not particularly limited, but it is contained in an amount of 1 × 10 ^-5 to 2 × 10 ^-2 mol per mol of silver halide. Is preferable, and the range of 5 × 10 ⁻⁴ to 5 × 10 ⁻³ mol is particularly preferable. When the compound of the general formula (I) or (II) of the present invention is contained in a photographic light-sensitive material, it is an aqueous solution when it is water-soluble, and alcohols (for example, methanol or ethanol) when it is water-insoluble, It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as esters (eg ethyl acetate) and ketones (eg acetone).

In the present invention, when the compound represented by formula (I) or (II) is contained in the photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic layers are contained. It may be contained in a hydrophilic colloid layer (eg, protective layer, intermediate layer, filter layer, antihalation layer, etc.). When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening and before coating. In particular, it is preferable to add it to the coating solution prepared for coating.

When the silver halide photographic light-sensitive material containing the compound represented by the general formula (I) or (II) of the present invention does not contain a hydrazine derivative as a nucleating agent, the light-sensitive material is represented by the general formula Most preferably, it is processed with a developer containing a developing agent represented by formula (III). This is because when treated with such a developing solution, the compound represented by formula (I) or (II) of the present invention itself acts as a so-called nucleating agent and gives a high contrast image. Incidentally, JP-A-5-53231 describes that a quaternary salt compound having a nitrogen-containing heterocyclic ring gives hard photographic characteristics. However, the compound represented by formula (I) or (II) of the present invention is described. Has a structure in which the adsorption-promoting group for silver halide represented by A is linked to a nitrogen-containing heterocyclic group quaternized with a linking group represented by L. Provides a high contrast enhancement effect.

Further, the compound represented by the general formula (I) or (I
When the silver halide photographic light-sensitive material containing the compound represented by I) simultaneously contains a hydrazine derivative as a nucleating agent, the light-sensitive material contains a developing agent represented by the general formula (III). May be treated with a liquid, or a developer containing a dihydroxybenzene-based developing agent as a main developing agent (particularly, a dihydroxybenzene-based developing agent and 1-
Developer containing a combination of phenyl-3-pyrazolidones or a developer containing a combination of a dihydroxybenzene-based developing agent and p-aminophenols). When the former developer is used, the compound represented by the general formula (I) or (II) of the present invention acts as both a nucleating agent and a nucleation accelerator, and a conventionally known quaternary salt heterocycle is used. Ultrahigh contrast photographic characteristics can be obtained as compared with the case where the compound is used. When the latter developer is used, the compound represented by the general formula (I) or (II) of the present invention acts as a nucleation accelerator having higher activity than conventionally known quaternary salt heterocyclic compounds. However, ultra-high contrast photographic characteristics can be obtained.

The compound represented by formula (III) will be described in detail.

[0055]

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In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P and Q represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are It represents an atomic group which is bonded to each other to form a 5- to 7-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. Y represents = O or = N-R _3,. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. General formula
In (III), R ₁ and R ₂ are each a hydroxy group,
Amino group (including a substituent having an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group, etc.), an acylamino group (acetylamino group, Benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), mercapto Base,
Represents an alkylthio group (methylthio group, ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group.

P and Q are hydroxy group, hydroxyalkyl group, carboxyl group, carboxyalkyl group, sulfo group, sulfoalkyl group, amino group, aminoalkyl group,
Represents an alkyl group, an alkoxy group, a mercapto group, or P and Q are bonded to each other, together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y; It represents an atomic group necessary for forming a 7-membered ring. Specific examples of the ring structure, -O -, - C (R 4) (R 5) -, -
_{C (R 6) =, -} C (= O) -, - N (R 7) -, - N
=, Combined. However, R ₄ , R ₅ , R
₆ , R ₇ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group, a sulfo group can be mentioned as the substituent), a hydroxy group,
Represents a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 7-membered ring include dihydrofuranone ring, dihydropyrone ring, pyranone ring, cyclopentenone ring, cyclohexenone ring, pyrrolinone ring, pyrazolinone ring, pyridone ring, azacyclohexenone ring, uracil ring and the like. And preferred examples of the 5- to 7-membered ring are:
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
The uracil ring can be mentioned.

Y is a group composed of ═O or ═N—R ₃ . Here, R ₃ is a hydrogen atom, a hydroxy group, an alkyl group (eg methyl, ethyl), an acyl group (eg acetyl), a hydroxyalkyl group (eg hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg sulfomethyl, sulfoethyl), carboxy. Represents an alkyl group (eg carboxymethyl, carboxyethyl). Specific examples of the compound represented by formula (III) are shown below, but the invention is not limited thereto.

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

[0063]

Embedded image

Of these, ascorbic acid or erythorbic acid (diastereomer of ascorbic acid) is preferred. The general range of the amount of the compound of the general formula (III) used is 5 × 10 ⁻³ per liter of the developing solution.
The amount is 1 to 1 mol, particularly preferably 10 ^{-2 to} 0.5 mol.

The developer containing the compound represented by the general formula (III) as a developing agent may further contain an auxiliary developing agent.

As auxiliary developing agents, dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone,
Bromohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, catechol, pyrazole, etc., 3-pyrazolidones (for example, 1 -Phenyl-3-pyrazolidone, 1-phenyl-
4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-4,4-dimethyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxymethyl-3-pyrazolidone, 1,
5-diphenyl-3-pyrazolidone, 1-p-tolyl-
3-pyrazolidone, 1-phenyl-2-acetyl-4,
4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone, 1-
(2-Benzothiazolyl) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc.), 3
-Aminopyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-
Amino-m-methylphenyl) -3-aminopyrazoline and the like) and phenylenediamines (for example, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4- Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfonamidoethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methoxyethylaniline and the like) can be added.

Further, even when aminophenols are used as an auxiliary developing agent, a high contrast image can be obtained.
As aminophenol developing agents, 4-aminophenol, 4-amino-3-methylphenol, 4- (N-
Methyl) aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N-
(2'-hydroxyethyl) -2-aminophenol,
Examples thereof include 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol, and hydrochlorides and sulfates of these compounds.

The developer containing the compound represented by the general formula (III) as a developing agent preferably contains an auxiliary developing agent. Among them, a p-aminophenol type developing agent and / or 1-phenyl-3 It preferably contains an auxiliary developing agent of the pyrazolidone type. The amount of these auxiliary developing agents used is generally in the range of 5 × 10 ⁻⁴ mol to 0.5 mol, preferably 10 ⁻³ mol to 0.1 mol, per liter of the developing solution.

Examples of the dihydroxybenzenes used in the developer containing the dihydroxybenzene type developing agent as the main developing agent include those mentioned above. This developer preferably contains an auxiliary developing agent together,
In particular, a developer in which a dihydroxybenzene-based developing agent and 1-phenyl-3-pyrazolidones are combined or a developer in which a dihydroxybenzene-based developing agent and p-aminophenols are combined is preferable. Examples of 1-phenyl-3-pyrazolidones and p-aminophenols include those mentioned above. The dihydroxybenzene type developing agent is usually used in an amount of 0.05 to 0.8 mol, preferably 0.2 to 0.6 mol, per liter of the developing solution. The auxiliary developing agent is preferably used in an amount of 0.06 mol or less, particularly 10 ⁻⁵ mol to 0.03 mol, per liter of the developing solution. A small amount of the compound represented by the general formula (III) as an antioxidant may be added to a developing solution containing a dihydroxybenzene type developing agent as a main developing agent. In this case, the amount of the compound represented by the general formula (III) added is 0.03 to 0.12 (compound of the general formula (III) / dihydroxybenzenes) in a concentration ratio with respect to the dihydroxybenzene type developing agent. Is preferred.

The components and conditions common to all the developing solutions used in the present invention will be described below. The developer preferably contains a preservative and an alkali in addition to the above essential components. Sulfite can be used as a preservative.
Examples of sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The addition amount of these sulfites is preferably 0.2 to 1.2 mol per liter of the developing solution.

As the alkaline agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used. As additives used in addition to the above, development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine, Development accelerators such as imidazole and its derivatives; mercapto compounds, imidazole compounds, benzotriazole compounds, benzimidazole compounds as antifoggants or black pep
per) inhibitor may be included. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-
Nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4-
Thiadiazol-2-yl) thio] zutansulfonate sodium, 5-amino-1,3,4-thiadiazole-
2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.05 to 2 mmol, per liter of the developing solution.

Various organic / inorganic chelating agents can be used in combination in the developer. As an inorganic chelating agent,
Sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as the organic chelating agent, mainly organic carboxylic acid, aminopolycarboxylic acid,
Organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. As the organic carboxylic acid, acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, asieleic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid , Itaconic acid, malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylene tetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, etc. JP-A-52-25632, 55-67
No. 747, No. 57-102624, and Japanese Patent Publication No. 53-53
The compounds described in the specification of No. 40900 and the like can be mentioned.

As the organic phosphonic acid, US Pat.
4454, 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730 and 54.
-112127, 55-4024, 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts. The amount of these chelating agents added is preferably 1 × 10 ⁻⁴ × 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ¹ mol per liter of the developing solution.
It is 10 ^-3 × 1 × 10 ^-2 mol. Further, if necessary, a color toning agent, a surfactant, an antifoaming agent, a hardener and the like may be contained.

The developer used in the present invention contains carbonate as a buffer, boric acid described in JP-A-62-186259, saccharides (for example, saccharose) and oximes described in JP-A-60-93433. (Eg acetoxime),
Phenols (for example, 5-sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt), aluminic acid (for example, sodium salt) and the like are used, and carbonate and borate are preferably used. The pH of the developer is 9.0
.About.11.5 is preferable, and particularly preferably 9.5 to 11.
The range is 0.

The development temperature and time are interrelated and are determined in relation to the total processing time. Generally, the development temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C.
The development time is 5 seconds to 2 minutes, preferably 7 seconds to 1 minute 30 seconds. When processing 1 square meter of a silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 500 ml or less, preferably 400 ml or less. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / liter. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH.
Modifiers (eg ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, fixing accelerators can be included. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants,
Examples thereof include amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added.
Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator,
For example, Japanese Examined Patent Publication Nos. 45-35754 and 58-12253.
5, thiourea derivatives described in JP-A Nos. 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in US Pat.
Examples include mesoionic compounds described in JP-A-229860, and compounds described in JP-A-2-44355 may be used. Examples of the pH buffering agent include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid and adipic acid, and inorganic acids such as boric acid, phosphate and sulfite. A buffer can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing the pH rise of the fixing agent due to the carry-in of the developing solution,
1.0 mol / liter, more preferably 0.02 to 0.
Use about 6 mol / liter. The pH of the fixer is 4.0
6.5 is preferable, and the range of 4.5 to 6.0 is particularly preferable. Further, as a dye elution accelerator, JP-A-64-
The compounds described in No. 4739 can also be used.

Hardeners in the fixing solution of the present invention include water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 mol to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is about 20 ° C to about 50 ° C, preferably 25 ° C.
~ 45 ° C, fixing time is 5 seconds to 1 minute, preferably 7 seconds to
50 seconds. The replenishing amount of the fixing solution is 600 ml / m ² or less, and particularly preferably 500 ml / m ² or less with respect to the processing amount of the light-sensitive material.

The photosensitive material which has been developed and fixed is then washed with water or stabilized. For washing or stabilizing treatment, the amount of washing water is usually ² per 1 m ^{2 of} silver halide light-sensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
It can also be carried out by including, that is, washing with water. That is, not only water saving processing is possible, but also piping for installing the automatic processing machine can be eliminated. As a method of reducing the replenishment amount of flush water, a multistage countercurrent method (for example, 2
Stages, 3 stages, etc.) are known. When this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed. Washed with water. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide washing tanks for squeeze rollers and crossover rollers described in No. 350 and No. 62-287252. Alternatively, addition of various oxidizing agents and filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Furthermore, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means according to the method according to the present invention is disclosed in JP-A-60- 23
As described in No. 5133, it can also be used for a processing solution having a fixing ability, which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, in order to prevent contamination by dyes eluted from the light-sensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in the washing tank. In addition, in some cases, stabilization treatment may be performed following the water washing treatment,
As examples thereof, JP-A-2-201357 and JP-A-2-132
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as the final bath of the light-sensitive material. If necessary, ammonium compounds, metal compounds such as Bi and Al, fluorescent whitening agents, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents can also be used in this stabilizing bath. Agents can also be added. Water used in the washing or stabilization process includes tap water, deionized water, halogen, water sterilized with ultraviolet germicidal lamps and various oxidizers (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time is 0-5
0 ° C. and 5 seconds to 2 minutes are preferable.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. The treatment liquid used in the present invention may be powdered or solidified. As the method, known methods can be used, but it is preferable to use the methods described in JP-A-61-259921, JP-A-4-85533 and JP-A-4-16841. Particularly preferred is the method described in JP-A-61-259921. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971, and is referred to simply as a roller-conveying type processor in this specification. The roller transport type processor has four steps of developing, fixing, washing and drying, and the method of the present invention also excludes other steps (for example, stopping step), but it is most similar to these four steps. preferable. Instead of the water washing step, four stable steps may be used.

As described above, the silver halide photographic light-sensitive material of the present invention may contain a hydrazine derivative as a nucleating agent. The hydrazine derivative has the general formula (I) or (I
It is preferable that the compound represented by the formula (I) is added to the same layer as the compound represented by the general formula (I) or (II).
It may be added to different layers. Preferred hydrazine derivatives for use in the present invention include compounds represented by the following general formula (IV).

[0083]

[Chemical 21]

In the general formula (IV), R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group or an amino group. Or represents a hydrazino group, and G ₁ is-
CO- group, -SO ₂ - group, -SO- group,

[0085]

[Chemical formula 22]

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

The general formula (IV) will be described in more detail. In the general formula (IV), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Moreover, this alkyl group may have a substituent. In the general formula (IV), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group. The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group and a hydroxy group. Group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having a hydrazide structure A group having a quaternary ammonium structure, an alkyl or aryl thio group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carboxyl group, a sulfo group, an acyl group, an alkoxy or aryloxy carbonyl group, a carbamoyl group, a sulfamoyl group, Examples include a rogen atom, a cyano group, a phosphoric acid amide group, a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure, and the like. As a preferred substituent, a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 20),
Aralkyl group (preferably 1 to 1 carbon atoms in the alkyl part)
3 monocyclic or bicyclic), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms),
Acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (Preferably having 1 to 3 carbon atoms
0) and so on.

In formula (IV), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
A 5- or 6-membered ring compound containing oxygen and a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. A pyridyl group or a pyridinium group is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable. Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
Hydrogen atom, alkyl group (for example, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (for example, o-hydroxybenzyl group, etc.), Aryl groups (eg phenyl groups, 3,5
-Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group and the like), and a hydrogen atom and trifluoromethyl group are particularly preferable. Also, G ₁ is -S
In the case of an O ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, , Dimethylamino group, etc.) are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferable.
As G in the general formula (IV), a -CO- group and a -COCO- group are preferable, and a -CO- group is most preferable. Also, R ₂ is G
The part of _1- R ₂ is split from the residual molecule, and -G ₁ -R ₂
It may be one that causes a cyclization reaction to form a cyclic structure containing a partial atom, and examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
Phenylsulfonyl group substituted to be 0.5 or more), acyl group having 20 or less carbon atoms (preferably benzoyl group, or substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (as the substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group Can be mentioned)). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (IV) may be further substituted, and preferable examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent ...
., May be multiply substituted, and preferred examples are also those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (IV) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁ or R _{2 in} the general formula (IV) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in US Pat.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048.
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Particularly preferred hydrazine derivatives in the present invention are those in which R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of silver halide grains, or a group having a quaternary ammonium structure or It is a phenyl group having an alkylthio group, G is a -CO- group, R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or a hydroxymethyl group at the 2-position). ) Is a hydrazine derivative. Any combination of the above R ₁ and R ₂ alternatives is possible and preferred.

Specific examples of the compound represented by formula (IV) are shown below. However, the present invention is not limited to the following compounds.

[0095]

[Chemical formula 23]

[0096]

[Chemical formula 24]

[0097]

[Chemical 25]

[0098]

[Chemical formula 26]

[0099]

[Chemical 27]

[0100]

[Chemical 28]

[0101]

[Chemical 29]

[0102]

[Chemical 30]

[0103]

[Chemical 31]

[0104]

[Chemical 32]

[0105]

[Chemical 33]

Examples of the hydrazine derivative used in the present invention include RESEARCH DISCLOSURE Item 2 in addition to the above-mentioned ones.
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442.
No. 2-220042, No. 2-221953, No. 2-221954, No. 2-285342, No. 2-2.
85343, 2-289843, 2-3027.
No. 50, No. 2-304550, No. 3-37642,
No. 3-54549, No. 3-125134, No. 3-1
No. 84039, No. 3-240036, No. 3-2400.
No. 37, No. 3-259240, No. 3-280038.
No. 3, No. 3-228536, No. 4-51143, No. 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
No. 5-45761, No. 5-45762, No. 5-45
No. 763, No. 5-45764, No. 5-45765,
The thing described in Japanese Patent Application No. 5-94925 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

The hydrazine derivatives of the present invention are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The silver halide emulsion used in the present invention may have a composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide or silver iodochlorobromide. As a method for preparing the silver halide emulsion used in the present invention, various methods known in the field of silver halide photographic light-sensitive materials are used. For example, P. Glafkides "Chimie et Physique Photographique" (Paul Mantel, 1967), GF Duffinu "GFDuffinu" Photographic E chemistry chemistry
mulsion Chemistry) (The F)
ocal Press), 1966), by VLZelikman et al., "Making and.
Coating Photographic Emulsion (Ma
kig and Coating Photographic Emulsion ”(published by The Focal Press, 1964) and the like. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 2
It is 0% or less, particularly preferably 15% or less. Here, the coefficient of variation is {(standard deviation of particle size) / (average particle size)} × 1
It is a numerical value represented by 00.

The average grain size of the grains in the monodisperse silver halide emulsion is 0.5 μm or less, particularly preferably 0.
It is 1 μm to 0.4 μm. As a method for reacting the water-soluble silver salt (silver nitrate aqueous solution) with the water-soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. As one form of the simultaneous mixing method, a method of keeping pAp constant in a liquid phase in which silver halide is produced, that is, a control double jet method can be used. Further, it is preferable to form grains using a so-called silver halide emulsion such as ammonia, thioether, substituted thiourea. Substituted thiourea compounds are more preferred, and JP-A Nos. 53-82408 and 55-7773 are preferred.
No. 7, etc. Preferred thiourea compounds are
Tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The control double jet method and the grain forming method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool. Monodisperse emulsion is a cube,
It preferably has a regular crystal form such as an octahedron or a tetradecahedron, and a cube is particularly preferable. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases.

In the present invention, a silver halide emulsion particularly suitable as a light-sensitive material for line drawing and halftone dot formation is silver 1
It is an emulsion produced in the presence of 10 ⁻⁸ to 10 ⁻⁵ mol of iridium salt or its complex salt per mol. In the present invention, a silver halide emulsion particularly suitable as a reversal light-sensitive material is a silver halide containing 90 mol% or more, and more preferably 95 mol% or more of silver chloride.
It is 0 mol% silver chlorobromide or silver chloroiodobromide. If the proportion of silver bromide or silver iodide is increased, the safety of safelight in a bright room is deteriorated or γ is decreased, which is not preferable.

The silver halide emulsion of the present invention may be chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination, for example,
The sulfur sensitizing method and gold sensitizing method, the sulfur sensitizing method, selenium sensitizing method and gold sensitizing method, the sulfur sensitizing method, tellurium sensitizing method and gold sensitizing method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds, for example, thiosulfates, thioureas, thiazoles, rhodanins and the like can be used. Can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The addition amount of the sulfur sensitizer changes under various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻³ mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-1.
3489, JP-A-4-25832, and 4-1092.
No. 40, No. 4-324855, etc. can be used. In particular, it is preferable to use the compounds represented by the general formulas (VIII) and (IX) in JP-A-4-324855.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride, which is presumed to be a sensitizing nucleus, on the surface or inside of the silver halide grain. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Laid-Open No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 4-129787, J. Chem. Soc. Chem. Commu
n., 635 (1980), ibid 1102 (1979), ibid 645 (1979), J. Chem. S.
oc.Perkin.Trans., 1, 2191 (1980), edited by S. Patai, The Ch
emistry of Organic Serenium and Tellurium Compound
The compounds described in s. Vo11 (1986) and Vo12 (1987) can be used. In particular, the compounds represented by formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferable.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions, etc., but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably 10 ⁻⁷ to 10 ⁻³
Use about mol. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer for use in the present invention include chloroauric acid, potassium chlorate, potassium Orichi isothiocyanate, include such gold sulfide, a 10 ^-7 to 10 ^-2 mol per mol of silver halide Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of forming silver halide grains or in the process of physical ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method shown in EP 293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, chemically sensitized ones). (Under different conditions) may be used together.

The silver halide photographic light-sensitive material of the present invention may contain a rhodium compound in order to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (I
II) Complex salt, hexabromorhodium (III) complex salt, hexaamminerhodium (III) complex salt, trizalatrodium (III)
Complex salts and the like can be mentioned. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used for stabilizing the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The total addition amount of the rhodium compound is 1 × 10 ^{-8 to} 5 × 1 per mol of the finally formed silver halide.
0 ^-6 mol is suitable, and preferably 5 x 10 ^-8 to 1 x 1
It is 0 ^-6 mol. The addition of these compounds can be appropriately carried out at the time of producing silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to be incorporated in the silver halide grains. preferable.

The silver halide photographic light-sensitive material of the present invention may contain an iridium compound in order to achieve high sensitivity and high contrast. As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like. These iridium compounds are used by dissolving them in water or a suitable solvent, and a method that is generally performed to stabilize the solution of the iridium compound,
That is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid,
Hydrofluoric acid, etc.) or alkali halides (eg KC
1, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The total amount of the iridium compound added is 1 × 10 ^{-8 to} 5 × per mol of the finally formed silver halide.
10 ⁻⁵ mol is suitable, and preferably 1 × 10 ⁻⁸ to 1 ×.
It is 10 ^-6 mol. The addition of these compounds can be appropriately carried out at the time of producing silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to be incorporated in the silver halide grains. preferable.

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper, lead and osmium. The metal is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention may contain at least one metal selected from rhenium, ruthenium and osmium. This content is 1 × 10 ⁻⁹ to 1 mol of silver.
The range of 1 × 10 ^-5 mol is preferable, and further 1 × 10 ^-8
The range of up to 1 × 10 ^-6 mol is preferred. These metals are 2
You may use together 1 or more types. These metals can be contained uniformly in the silver halide grains, and JP-A-63-
29603, JP-A-2-306236, 3-16.
No. 7545, No. 4-76534, and Japanese Patent Application No. 4-6830.
No. 5, No. 4-258187, etc., it is also possible to allow the particles to have a distribution. Rhenium, ruthenium and osmium are disclosed in JP-A-63-204.
No. 2, JP-A Nos. 1-285941 and 2-20852.
No. 2-20855, etc., and is added in the form of a water-soluble complex salt. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML6] ^-n Here, M represents Ru, Re, or Os, and n represents 0, 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Further, preferred ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl ligands, thionitrosyl ligands and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^-3 [ReBr ₆ ] ^-3 [ReCl ₅ (NO)] ^-2 [Re (NS) Br ₅ ] ^-2 [Re (NO) (CN) ₅ ] ^-2 [Re (O ) ₂ (NO) ₄ ] ^-3 [RuCl ₆ ] ^-3 [RuCl ₄ (H ₂₀ ) ₂ ] ^-1 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS)] ^-2 [Ru (CN) ₆ ] ^-4 (Ru (CO) ₃ Cl ₃ ) ^-2 (Ru (CO) Cl ₅ ) ^-2 (Ru (CO) Br ₅ ) ^-2 (OsCl ₆ ) ^-3 (OsCl ₅ (NO)) ^-2 Os (NO) (CN) ₅ ] ^-2 [Os (NS) Br ₅ ] ^-2 [Os (CN) ₆ ] ^-4 [Os (O) ₂ (CN) ₄ ] ^-4

The addition of these compounds can be appropriately carried out at the time of producing the silver halide emulsion grains and at each stage before coating the emulsion.
It is preferably incorporated into silver halide grains. To incorporate these compounds into the silver halide grains by adding them during grain formation of silver halide, a metal complex powder or an aqueous solution dissolved with NaCl or KCl is used as a water-soluble salt or water-soluble salt during grain formation. A method of adding it to a halide solution, or a method of preparing a silver halide grain by a method of adding a third solution when a silver salt and a halide solution are simultaneously mixed, and a three-liquid simultaneous mixing, or during grain formation. In addition, there is a method in which a necessary amount of an aqueous solution of a metal complex is charged into a reaction vessel. Particularly preferred is a method of adding powder or an aqueous solution dissolved together with NaCl and KCl to the water-soluble halide solution. To add to the surface of the particles, a necessary amount of the aqueous solution of the metal complex may be added to the reaction vessel immediately after the particles are formed, during or after the physical aging, or at the time of the chemical aging. The silver halide grain in the present invention may be doped with another heavy metal salt. In particular, K ₄ [Fe (C
N) ₆ ] is preferably used for doping the Fe salt. Further, in the present invention, other metals included in Group VIII, namely, cobalt, nickel, iridium, palladium,
You may use platinum etc. together. In particular, the combined use with iridium salts such as iridium chloride and ammonium hexachloroiridium (III) is advantageous because a high-sensitivity and high-contrast emulsion can be obtained.

A spectral sensitizing dye selected depending on the exposure wavelength can be added to the silver halide emulsion layer used in the present invention. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-A.
Item (p.23, December 1978), Item 1831X
Section (p.437, August 1978) or cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. The content of the sensitizing dye of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, the type of antifoggant compound, and the like. It is desirable to select the optimum amount accordingly, and the test method for the selection is well known to those skilled in the art. Usually, it is preferably used in the range of 10 ^-7 to 1 × 10 ^-2 mol, particularly 10 ^-6 to 5 × 10 ^-3 mol per mol of silver halide.

As the binder for the protective colloid of the photographic emulsion or the other hydrophilic colloid layer of the emulsion layer, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Such;
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetrazaindenes), pentaazaindenes, etc .; Hydroquinone and its derivatives; Disulfides such as thioctic acid; As antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many known compounds can be added. Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

The light-sensitive material of the present invention may contain an organic desensitizer. Preferred organic desensitizers have at least one water-soluble group or alkali-dissociable group. These preferred organic desensitizers are exemplified in US Pat. No. 4,908,293. When an organic desensitizer is used, 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / m ² , in the silver halide emulsion layer,
It is suitable to make it exist in the range of 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁵ mol / m ² .

The light-sensitive material of the present invention may contain a development accelerator. Suitable development accelerators or nucleation-infectious development accelerators for use in the present invention are disclosed in JP-A-53-77616.
No. 54-37732, No. 53-137133,
In addition to the compounds disclosed in JP-A-60-140340 and JP-A-60-14959, various compounds containing N or S atoms are effective. The optimum addition amount of these accelerators varies depending on the type of compound, but is 1.0 × 10 ^{−3 to} 0.
5 g / m ^2, preferably it is desirable to use a range of ^{5.0 × 10 -3 ~0.1g / m 2} . These accelerators are dissolved in a suitable solvent (H ₂ O) alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution. You may use these additives together in multiple types.

The emulsion layer of the present invention or the other hydrophilic colloid layer may contain a dye as a filter dye or for various purposes such as prevention of irradiation. As a filter dye, a dye for further lowering photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, and safety against safelight light when handled as a light-sensitive room light material A dye having a substantial light absorption mainly in the region of 310 nm to 600 nm is used for enhancing the light emission. These dyes are added to the emulsion layer according to the purpose, or added together with a mordant to the upper part of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support. It is preferable to fix it before use. Usually 10 ^-3 g / m ^{2 to} 1 g, though it depends on the molar absorption coefficient of the dye
/ M ² It is added in the range. Preferably 10 mg to 500 mg
/ M ² . The above dye can be added to the coating solution after being dissolved or dispersed in an appropriate solvent [for example, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof]. These dyes can be used in combination of two or more kinds. Specific examples of these dyes are described in US Pat. No. 4,908,293. In addition, U.S. Pat. Nos. 3,533,794 and 3,314,794,
U.S. Pat. No. 3,352,681, JP-A-46-2784, U.S. Pat. Nos. 3,705,805, and 3,707,375.
No. 4,045,229, 3,700,455
No. 3,499,762, West German patent application publication 1,5
UV absorbing dyes described in, for example, No. 47,863 are also used. In addition, pyrazolone oxonol dyes described in US Pat. No. 2,274,782, US Pat.
956,879, diarylazo dyes, US Pat. Nos. 3,423,207 and 3,384,487, styryl dyes and butadienyl dyes, and US Pat. No. 2,527,583. Merocyanine dyes, US Pat. Nos. 3,486,897 and 3,652,284
No. 3,718,472, merocyanine dyes and oxonol dyes, and US Pat. No. 3,976,661.
No. 584,609, No. 1,177,429, JP-A Nos. 48-85130, 49-99620, and 49-
114420, US Pat. Nos. 2,533,472, 3,148,187, and 3,177,078,
No. 3,247,127, No. 3,540,887,
The dyes described in Nos. 3,575,704 and 3,653,905 can also be used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium yoban, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldeside, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane). Etc.), active vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids ( Mucochloric acid, mucophenoxycyclo acid, etc.), epoxy compounds (tetramethylene glycol diglycidyl ether, etc.), isocyanate compounds (hexamethylene diisocyanate, etc.), etc. can be used alone or in combination. Also, JP-A-56-66841
U.S. Pat. No. 1,322,971 and U.S. Pat. No. 3,67
The polymer hardeners described in No. 1,256 can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced according to the present invention has a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Contrast enhancement, sensitization), and various other surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (eg polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives ( Non-ionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alk Such as taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., such as carboxy group, sulfo group, phorpho group, sulfate ester group, phosphate ester group, etc. Anionic surfactants containing acidic groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acids or phosphoric acid esters, alkylbetaine acids, amine oxides; alkylamine hydrochloric acid, aliphatic or aromatic primary surfactants. Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Particularly, the surfactant preferably used in the present invention has a molecular weight of 60 described in JP-B-58-9412.
It is 0 or more polyalkylene oxides. Also, a polymer latex such as a polyalkyl acrylate may be incorporated for dimensional stability.

The present invention may include a conductive metal oxide. The conductive metal oxides are crystalline metal oxide particles, but generally include those containing oxygen vacancies and those containing a small amount of different atoms forming donors with respect to the metal oxide used. It is particularly preferable because it has high conductivity, and the latter is particularly preferable because it does not cause fog in the silver halide emulsion. Examples of metal oxides are ZnO, TiO ₂ , SnO ₂ ,
_{Al 2 O 3, In 2 O} 3, SiO 2, MgO, BaO, MoO 3, V 2 O 5 or the like, or composite oxides thereof may, in particular ZnO, TiO ₂ and Zn
O ₂ is preferred. As an example containing a heteroatom, for example, ZnO
It is effective to add Al, In and the like, to SnO ₂ , Sb, Nb and a halogen element, and to TiO ₂ to add Nb and Ta.

The addition amount of these hetero atoms is 0.01 mol%
To 30 mol% is preferable, and 0.1 mol% to 1 is particularly preferable.
The range of 0 mol% is preferred. The metal oxide fine particles of the present invention have conductivity, and their volume resistivity is 107 Ω ^-cm.
It is particularly preferable that it is 105 Ω- ^cm or less. Regarding these oxides, JP-A-56-143431,
56-120519, 58-62647 and the like. Furthermore, as described in JP-B-59-6235, a conductive layer material obtained by adhering the above-mentioned metal oxide to other crystalline metal oxide particles or fibrous material (for example, titanium oxide) may be used. . The particle size that can be used is preferably 10 μm or less, but when it is 2 μm or less, stability after dispersion is good and it is easy to use. Further, in order to make the light scattering property as small as possible, it is very preferable to use the conductive particles of 0.5 μm or less because a transparent photosensitive material can be formed. When the conductive material is needle-like or fibrous, the length is preferably 30 μm or less and the diameter is 2 μm or less, particularly preferably the length is 0.5 μm to 25 μm or less, and the length / diameter ratio is Is 3 or more. In the present invention, these conductive metal oxides are preferably added to the antihalation layer, back layer and undercoat layer.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 See page 17, lower left column, line 20, and further JP-A Nos. 1-112235, 2-48653, 2-105135, 2-124560, 3-7928, and 3-67242. No. 5-11389, Japanese Patent Application No. 3-41 1064, and No. 4-354748, the spectral sensitizing dyes. 2) Nucleation accelerator A compound represented by the general formula (I), (II), (III), (IV), (V) or (VI) described in Japanese Patent Application No. 4-237366. JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 from general formulas (II-m) to (II-p) and compounds II-1 or II-22, Compounds described in JP-A-1-179939. 3) Surfactant, antistatic JP-A-2-12236, page 9, upper right column, line 7 to agent, same as lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to same Page 4, lower right column 18, line 18. 4) Antifoggants and Stabilizers JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5 Furthermore, the thiosulfinic acid compounds described in JP-A-1-237538. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compounds having an acid group JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and page 2-55349, page 8 lower right column, line 13 To page 11, upper left column, line 8. 7) Matting agent, slipping agent, possible JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 8) Hardeners, JP-A-2-103536, page 18, upper right column, lines 5 to 17; 9) Dyes, JP-A-2-103536, page 17, lower right column, lines 1 to 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5. Furthermore, the solid dyes described in JP-A-2-294638 and JP-A-5-11382. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compounds Compounds represented by formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), and general formula (R in pages 3 to 20 of JP-A No. 3-174143) -1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application No. 3-69466 and Japanese Patent Application Laid-Open No. 4-278939. 13) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 14) Dihydroxybenzene Compounds described in JP-A-3-39948, page 11, upper left column to category 12, page 12 lower left column, and European Patent No. 452,772A.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[0139]

【Example】

Example 1 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion A was prepared by the following method. [Emulsion A] Aqueous silver nitrate solution, potassium bromide, sodium chloride, and K ₃ corresponding to 3.5 × 10 ^-7 mol per mol of silver
An aqueous solution of a halogen salt containing IrCl ₆ and K ₂ Rh (H ₂ O) Cl ₅ corresponding to 2.0 × 10 ⁻⁷ mol, sodium chloride, and 1,3-
The mixture was added to a gelatin aqueous solution containing dimethyl-2-imidazolidinethione by a double jet method with stirring to prepare silver chlorobromide grains having an average grain size of 0.25 μm and a silver chloride content of 70 mol%.

Thereafter, the product was washed with flocculation according to a conventional method, 40 g of gelatin was added per 1 mol of silver, and 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver.
Adjusted to H6.0 and pAg7.5, 2mg per mol of silver
6 of sodium thiosulfate and 4 mg of chloroauric acid
Chemical sensitization was performed so that the optimum sensitivity was obtained at 0 ° C. Then, 4-hydroxy-6-methyl-1,3,3 as a stabilizer
150 mg of a, 7-tetrazaindene was added, and further 100 mg of proxel was added as a preservative. The obtained grains each have an average grain size of 0.25 μm and a silver chloride content of 7
It was 0 mol% of silver chlorobromide cubic grains. (Variation coefficient 1
0%)

Preparation of Coating Sample A polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride was applied in order from the support side so as to have a layer structure of UL layer, EM layer, PC layer, OC layer, Samples 101 to 120 were prepared. The preparation method and coating amount of each layer are shown below.

(UL layer) A dispersion of polyethyl acrylate in an amount of 30 wt% with respect to gelatin was added to an aqueous gelatin solution and coated so as to have a gelatin content of 0.5 g / m ² .

[0143] in (EM layer) above emulsions A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2), further 3 × 10 ^-4 mol of mercapto compound represented by the following (a), 4 × 10 ^-4 mol of mercapto compound represented by (b), and 4 × 10 ^-4 mol of (c) per 1 mol of silver The triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline was added. Further, the onium salt compound of the present invention and the following comparative compound were added as shown in Table 1. Furthermore, hydroquinone 100 mg, N-oleyl-
N-Methyltaurine sodium salt was added so as to be coated at 30 mg / m ² . Then, the hydrazine derivative IV-3
8 was added so that 10 mg / m ^{2 was} applied, followed by (d)
Is 200 mg / m ² , the dispersion of polyethyl acrylate is 400 mg / m ² , and the average particle size is 0.
Colloidal silica 200 mg / m ² of 02Myuemu, 1,3-vinylsulfonyl-2-propanol further as a hardening agent were added 200 mg / m ^2. The pH of the solution was adjusted to 5.65 with acetic acid. Coating them with a silver amount of 3.5 g / m ²
Was applied.

[0144]

Embedded image

[0145]

Embedded image

[0146] (PC layer) dispersion of 50 wt% of ethyl acrylate with respect to gelatin in the gelatin solution and ethyl sulfonate sodium 5 mg / m ^2, 1,5-dihydroxy-2-benzaldoxime a 10 mg / m ² It was added so that it was coated, and gelatin was coated at 0.5 g / m ² .

(OC layer) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 40 having an average particle size of about 3.5 μm 40
mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² , silicone oil 20 mg / m ^2, and a fluorosurfactant 5 mg / m ^{2 represented by the following} structural formula (e) as a coating aid. 100 mg / m ² of sodium dodecylbenzene sulfonate was applied.

[0148]

Embedded image

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0150]

Embedded image

Dye Mixture of dye [a], dye [b] and dye [c] Dye [a] 70 mg / m ² Dye [b] 70 mg / m ² Dye [c] 90 mg / m ²

[0152]

[Chemical 38]

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfone Sodium acid salt 15mg / m ² Sodium acetate 40mg / m ²

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was exposed to xenon flash light having an emission time of 10 ⁻⁵ sec through a step wedge through an interference filter having a peak at 488 nm. After developing with the developer A at 35 ° C. for 30 seconds, fixing, washing with water and drying were performed. A fixing solution having the following composition was used as the fixing solution.

Developer A Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0.08 g 4 -Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenz Imidazole-5-sulfonic acid sodium salt 0.15 g Potassium hydroxide and water were added to make 1 liter, and the pH was adjusted to 1
Adjust to 0.5.

Fixing solution Ammonium thiosulfate 359.1 ml Ethyleneaminetetraacetic acid 2Na dihydrate 2.26 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulphate 25.3 g Water was added to 1 liter pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 (2) Evaluation of image contrast As an index (gamma) indicating image contrast, the characteristic curve The point of fog + concentration of 0.3 to the point of fog + concentration of 3.0 was connected by a straight line, and the slope of this straight line was expressed as a gamma value. That is, gamma = (3.0-0.3) / [log
(Exposure amount that gives a density of 3.0)-(exposure amount that gives a density of 0.3)], and the larger the gamma value, the harder the photographic characteristics are. (3) Evaluation of halftone dot quality (DQ) The halftone dots of the light-sensitive material exposed through the contact screen were observed with a magnifying glass, and the sharpness and smoothness were evaluated on a 5-point scale.
"5" represents the best level for both sharpness and smoothness, and "1" represents the lowest level. When the level is "3" or more, the sharpness and smoothness of the on / off portion of the image when the scanner is actually exposed is practically acceptable. (4) Evaluation of black spots The exposed light-sensitive material was developed with the developer A at 35 ° C. for 90 seconds, and then fixed, washed with water and dried,
The light-sensitive material was observed with a magnifying glass, and the generation level was evaluated on a scale of 5 levels.
"5" represents a level in which no occurrence has occurred, and "1" represents a minimum level. A level of "3" or higher is practically acceptable. (5) Evaluation of sensitivity The sensitivity was shown by the relative value of the reciprocal of the exposure amount giving a density of 1.5. The sensitivity of the sample of Comparative Example (0) was set to 100.

The above results are shown in Table 1.

[0158]

[Table 1]

<Results> As can be seen from Table 1, when the hydrazine compound is used in combination with the onium compound of the present invention, the photographic performance is better than that in the case where the conventional compound is used in combination.

Example 2 Sample 101 was prepared in the same manner as in Example 1 except that Developer B having the following composition was used in place of Developer A used in Example 1.
As a result of evaluation of 120 to 120, the same good results as in Example 1 could be obtained.

Developer B Sodium hydroxide 10.0 g Diethylenetriamine-pentaacetic acid 1.5 g Potassium carbonate 15.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.10 g 1-Phenyl-5-mercaptotetrazole 0.02 g Sulfurous acid Potassium 10.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.40 g Sodium erythorbate 30.0 g Potassium hydroxide is added and water is added to make 1 liter p.
Adjust H to 10.5. Example 3 <Preparation of silver halide photographic light-sensitive material> Samples 201 to 220 were prepared in the same manner as in Example 1 except that the sensitizer did not contain the hydrazine derivative IV-38.

<Evaluation of Photographic Performance> The same procedure as in Example 1 was carried out except that the developer B and the developer C having the following formulation were used in place of the developer A used in Example 1.

Developer C (Comparative Example) Sodium hydroxide 10.0 g Diethylenetriamine-pentaacetic acid 1.5 g Potassium carbonate 15.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.10 g 1-Phenyl-5-mercaptotetrazole 0.02 g potassium sulfite 10.0 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.40 g hydroquinone 15.3 g potassium hydroxide is added, and water is added to make 1 liter p.
Adjust H to 10.5.

Image contrast and halftone dot quality (D
The evaluation of Q) was performed in the same manner as in Example 1.

The results are shown in Table 2.

[0166]

[Table 2]

<Results> As can be seen from Table 2, the compounds of the present invention were found to exhibit good photographic performance in combination with the developers of the present invention. Even with the developer of the present invention,
Good performance cannot be obtained with the comparative compound.

Example 4 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion B was prepared by the following method. [Emulsion C] An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed in an aqueous gelatin solution kept at 40 ° C. in the presence of 5.0 × 10 ^-6 mol of NH ₄ RhCl ₆ per 1 mol of silver, which was well known in the art. After removing the soluble salt by the method described above, gelatin was added, and 2-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer without chemical ripening. This emulsion has an average grain size of 0.2
It was a monodisperse emulsion having a cubic crystal shape of μ.

Preparation of Coating Sample Sample 3 was coated on a polyethylene terephthalate film support having a moisture-proof layer undercoat containing vinylidene chloride so as to have a layer structure of an EM layer and a PC layer sequentially from the support side.
01-320 was created. The preparation method and coating amount of each layer are shown below. [EM Layer] To this emulsion B, as shown in Tables 3 and 4, the onium salt compound of the present invention and the comparative compound were added. Then, the hydrazine derivative IV-33 was added at 20 mg / m ² .

Further, polyethyl acrylate latex was added in a solid content of 30 wt% with respect to gelatin, 1,3-di-vinylsulfonyl-2-propanol was added as a hardening agent, and 3.8 g / m 2 was added on the polyester support. ^It was applied so that the Ag amount was ² . The gelatin was 1.8 g / m ² . [PC Layer] Gelatin 1.5 g / m ^2, was coated with a layer of polymethyl methacrylate 0.3 g / m ² of particle size 2.5 [mu].

The base used in this example has a back layer and a back protective layer having the following compositions. Here, the swelling ratio on the back side is 110%. (Back layer formulation) Gelatin 170 mg / m ² Sodium dodecylbenzene sulfonate 32 mg / m ² Dihexyl-α-sulfosuccinate sodium 35 mg / m ² (Back protective layer formulation) Gelatin 2.8 g / m ² Silicon dioxide matting agent (average) Particle size 3.5 μm) 26 mg / m ² Dihexyl-α-sulfosuccinate sodium 20 mg / m ² Sodium dodecylbenzenesulfonate 67 mg / m ²

[0172]

[Chemical Formula 39]

[0173]

[Chemical 40]

Ethyl acrylate latex (average particle size 0.05 μm) 260 mg / m ² 1,3-divinylsulfonyl-2-propanol 149 mg / m ²

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The obtained sample was exposed through a step wedge with a bright room printer P-627FM manufactured by Dainippon Screen Co., Ltd. Automatic processor FG710NH
Was developed at 38 ° C. for 20 seconds with the developer A described in Example 1, fixed with the fixer described in Example 1, washed with water and dried. (2) Evaluation of Sensitivity, DQ, and Image Contrast The same procedure as in Example 1 was performed.

(3) Evaluation of Image Quality of Extracted Characters When the image quality of extracted characters is 5, it means that 50% of the halftone dot area is 50% of the halftone dot area on the return sensitive material using the original as shown in FIG. The image quality is such that a character with a width of 30 μm can be reproduced when an appropriate exposure is performed, and it is a very good quality of a blank character. On the other hand, a blank character image quality of 1 is an image quality in which only an image having a width of 150 μm or more can be reproduced when an appropriate exposure is given as in the above case. A sensory evaluation ranked between 4 and 2 between 5 and 1.
A level of 3 or more is a practical level.

The results are shown in Table 3.

[0178]

[Table 3]

<Results> As can be seen from Table 3, it was found that the combined use of the compound of the present invention with the hydrazine compound exhibits better photographic performance than the combined use of the conventional compound. Example 5 Samples 301 to 320 were evaluated in the same manner as in Example 4 except that the developing solution B was used instead of the developing solution A used in Example 4, and the same favorable results as in Example 1 were obtained. I was able to get Example 6 <Preparation of silver halide photographic light-sensitive material> Samples 401 to 420 were prepared in the same manner as in Example 4 except that the sensitizer did not contain the hydrazine derivative IV-33. <Evaluation of Photographic Performance> The same procedure as in Example 1 was performed except that the developer B and the developer C described above were used instead of the developer A used in Example 3.

The results are shown in Table 4.

[0181]

[Table 4]

<Results> As can be seen from Table 4, the compounds of the present invention were found to exhibit good photographic performance in combination with the developers of the present invention. Even with the developer of the present invention,
Good performance cannot be obtained with the comparative compound.

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration at the time of exposure when a blank character image is formed by overlapping and reversing, each reference numeral indicates the following. (A) Transparent or semi-transparent embedment base (b) Line drawing original (black part shows line drawing) (c) Transparent or semi-transparent embedding base (d) Halftone dot manuscript (black part is halftone dot) (E) Photosensitive material for flipping back (note that the shaded area indicates the photosensitive layer)

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one compound represented by the following general formula (I) or (II). Embedded image In the formula, A represents an adsorption promoting group to silver halide or a precursor thereof, and B represents a quaternized nitrogen-containing heterocyclic group and a counter ion thereof. L represents a linking group, and m is 0
Alternatively, 1 and n represent an integer of 1 to 4. 2. The silver halide photographic light-sensitive material according to claim 1, further comprising a hydrazine derivative. 3. An image characterized by being developed with a developer containing a developing agent represented by the following general formula (III) after exposing the silver halide photographic light-sensitive material of claim 1 or 2. Forming method. Embedded image In the formula, R ₁ and R ₂ are each a hydroxy group, an amino group,
It represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P, Q
Is a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group,
It represents a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are bonded to each other and two vinyl carbon atoms substituted by R ₁ and R ₂ are substituted by Y. Represents an atomic group forming a 5- to 7-membered ring together with the carbon atom. Y is = O or, = N-R ₃
Represents R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. 4. An image forming method, which comprises exposing the silver halide photographic light-sensitive material according to claim 2 to exposure and then developing it with a developer containing a dihydroxybenzene-based developing agent.